WO2010086094A1

WO2010086094A1 - Method for introducing carbon particles into a polyurethane surface layer

Info

Publication number: WO2010086094A1
Application number: PCT/EP2010/000220
Authority: WO
Inventors: Stephanie Vogel
Original assignee: Bayer Materialscience Ag
Priority date: 2009-01-30
Filing date: 2010-01-16
Publication date: 2010-08-05
Also published as: KR20110123251A; EP2391671B1; JP2012516362A; TW201037016A; US20110281071A1; RU2011135869A; SG173040A1; CN102300911A; CA2750943A1; EP2213699A1; EP2391671A1

Abstract

The invention relates to a method for introducing electrically conductive carbon particles into a surface layer comprising polyurethane. These carbon particles can in particular be carbon nanotubes. In the method according to the invention, a solution of non-aggregated carbon particles having a mean particle diameter of = 0.3 nm to = 3000 nm acts in a solvent upon a surface layer comprising polyurethane. The solvent is able to cause the maceration of a surface layer comprising polyurethane. The dwell time is measured such that it is not sufficient to carry the polyurethane over into the solution. The invention furthermore relates to a polyurethane layer that comprises electrically conductive carbon particles and can be obtained by means of a method according to the invention. The invention likewise relates to a polyurethane object having surface layer comprising electrically conductive carbon particles, obtainable by a method according to the invention.

Description

Method of introducing carbon particles into a polyurethane surface layer

The present invention relates to a method for introducing electrically conductive carbon particles into a surface layer comprising polyurethane. These carbon particles may in particular be carbon nanotubes. It further relates to a polyurethane layer which comprises electrically conductive carbon particles and is obtainable by a method according to the invention. The invention further relates to a polyurethane article having a surface layer comprising an electrically conductive carbon particle obtainable by a method according to the invention.

Carbon nanotubes (CNTs) are known for their exceptional properties. For example, their strength is about 100 times that of steel, whose thermal conductivity is about twice that of diamond, their thermal stability reaches up to 2800 ⁰ C in a vacuum and their electrical conductivity can be many times that of

Conductivity of copper amount. These structural characteristics are on a molecular level

Level, however, only accessible if it is possible to distribute carbon nanotubes homogeneously and produce the largest possible contact between the tubes and the medium, so make them compatible with the medium and thus stable to disperse. With regard to electrical conductivity, it is furthermore necessary to form a homogeneous network of tubes, in which they ideally only touch at the ends. This should be the

Carbon nanotubes as isolated as possible, that is agglomerate-free, not aligned and present in a concentration at which such a network can just form, resulting in the sudden increase in electrical conductivity as a function of the

Concentration of carbon nanotubes reflects (percolation limit).

For technical applications, therefore, the incorporation of such particles in polymer matrices is of interest. Two aspects have to be taken into account for the successful processing of carbon nanotubes, for example, if one wants to make a material electrically conductive by their use: the complete breaking up and unbundling of carbon nanotube agglomerates and the suppression of the great tendency of carbon nanotubes to reagglomeration (in one and the same Medium during the aging process or during the processing of such a dispersion to the finished material). These difficulties in carbon nanotube processing are due to the hydrophobic character of the carbon nanotube surface and the high aspect ratio of this quasi one-dimensional structure.

Should now be avoided that carbon nanotubes in the form of bundles and / or

Agglomerates find an energetic minimum, their compatibility with the surrounding medium must be increased. However, it should be noted that a chemical, Although covalent functionalization of carbon nanotubes can improve their compatibility with the medium. This manifests itself for example in an increased (thermal) long-term stability and the absence of reagglomeration during, for example, polyurethane production. However, this surface modification also interrupts the delocalized π-electron system of the tube and thus lowers the electrical conductivity of each individual tube as a function of the degree of functionalization.

The non-covalent functionalization of carbon nanotubes by, for example, dispersing additives provides an alternative to the chemical, covalent modification and compatibilization of the tube with the medium. However, it should be noted that for any new medium, whether polyurethane raw material or formulation requires new optimization with regard to the chemistry and the concentration of the respective dispersing additive and can never represent a universal solution.

Finally, it should be noted that any processing of fillers, including carbon nanotubes, also carries risks in that it may be possible to achieve a new property, such as electrical conductivity, while at the same time degrading several other mechanical properties. This is mainly due to the fact that the taxpayers are not taxed. komnakt.e and / or elastic systems are incorporated. Residual agglomerates which could not be completely broken up during the dispersing process represent, for example, a predetermined breaking point in a compact molded part. Mechanical properties such as, for example, the impact strength and breaking strength are impaired by such agglomerates. With the intention now to make a compact material by the addition of carbon nanotubes electrically conductive, should be distributed homogeneously over the entire volume of the material carbon nanotubes according to the prior art, so that the percolation limit is exceeded and at the same time no residual agglomerates are present.

This procedure very often fails already due to the dramatic increases in viscosity, which are due to the carbon nanotubes concentrations required for exceeding the percolation limit. Furthermore, the reagglomeration of homogeneously dispersed carbon nanotubes during polyurethane processing with this method can not be excluded and easily prevented.

In connection with the processing of carbon nanotubes in (thermoplastic) polyurethanes, numerous works are known from the literature in which the finished polymer is first completely dissolved in an organic solvent, then the nanotube dispersion is carried out in this polymer solution and the resulting nanotube dispersion on polyurethane / Solvent base is drawn into a film or poured into a mold. Of the The last step in these processes is in each case the lengthy evaporation of the large amounts of solvent. Examples can be found in the following publications: NG Sahoo, YC Jung, HJ. Yoo, JW Cho, Composites Science and Technology 2007, 76, 1920-1929; NG Sahoo, YC. Young, HJ. Yoσ, JW Cho, Macromol. Chem. Phys. 2006, 207, 1773-1780; Xu, T. Zhang, B. Gu, J. Wu, Q. Chen Macromolecules 2006, 39, 3540-3545; J. Deng, J. Cao, J. Li, H. Tan, Q. Zhang, Q. Fu, Journal of Applied Polymer Science 2008, 108, 2023-2028; RN Jana, JW Cho Journal of Applied Polymer Science 2008, 108, 2857-2864 and X. Wang, Z. Du, C.Zhang, C.Li, X. Yang, H.Li, Journal of Polymer Science: Part A: Polymer Chemistry 2008, 46, 4857-4865 and in US 2005/0127329 Al.

An overview of this field is also found in N. Grossiord, J. Loos, O. Regev, C.E. Koning, Chem. Mater., 2006, 18 (5), 1089-1099.

Furthermore, processes are known from the literature (BS Shim, W. Chen, C. Doty, C. Xu, NA Kotov, Nano Lett. 2008, 8 (12), 4151-4157), in which cotton fibers in carbon nanotube dispersions based on ethanolic Nafion Solution or aqueous PSS solution. As a result, the carbon nanotubes irreversibly adsorb to the surface of the fiber, forming a homogeneous coating and thus give this fiber electrical conductivity.

Fugetsu et al. (Carbon 2008, ASAP, doi: 10.1016 / j.carbon.2008.11.013) established a process in which polyester fibers were passed through a dip bath and coated on the surface with CNTs. For this purpose, multi-walled carbon nanotubes in aqueous solution were first dispersed by means of surfactants and then mixed with an anionic polyurethane dispersion. The immersion bath temperature was 40 ^° C. The immersed fiber was then heated for 30 seconds in an oven at 170 ^° C. (100 ^° C. above the glass transition temperature of the polyester fiber). Depending on the nanotube concentration, such modified fibers had electrical conductivities even after washing with water in the area of interest for antistatic applications.

A possible alternative is the approach not to equip the entire polymer matrix, but only with a directly adjacent to the surface material layer with the particles. Such an approach would be desirable to avoid the disadvantages of solvent consumption and viscosity increase described above.

The invention therefore proposes a method for introducing electrically conductive particles into a surface layer comprising polyurethane, comprising the steps:

(A) providing a solution of unaggregated carbon particles having an average particle diameter of> 0.3 nm to <3000 nm in a solvent capable of causing the swelling of a surface layer comprising polyurethane;

(B) contacting the surface layer comprising polyurethane with the solution of carbon particles;

(C) exposing the carbon particles to the polyurethane-containing surface layer for a period of time insufficient to dissolve the polyurethane;

(D) terminating the action of the solution of the carbon particles on the surface layer comprising polyurethane.

Electrically conductive particles in the meaning of the present invention are initially all particles of a material which is not an insulator. Typically, insulators are substances having an electrical conductivity of less than 10 ^-8 S / m. The particles are incorporated in a surface layer comprising polyurethane, which means that it is not only the surface itself that is occupied by the particles, but also that the material lying directly below the surface absorbs the particles. Accordingly, in the context of the invention, the term surface layer, as opposed to the two-dimensional surface, means a three-dimensional layer of material which includes the surface as one of its boundaries. The surface layer is delimited to the interior of the object in question at least by the fact that it contains just the electrically conductive particles.

The polyurethane (PUR) itself may initially be any polyurethane and may contain the usual additives such as fillers, flame retardants and the like. Examples of polyurethane classes are PU foams including foamed polyurethanes with a very high density of more than 600 kg / m ³ , PUR casting resins, PUR cast elastomers and thermoplastic PUR (TPU).

It is possible and preferred that the surface layer is associated with a molded part or semifinished product such as foils, tubes or sheets comprising a polyurethane. The polyurethane is thus generally not present as a polymer dispersion.

Step (A) involves providing a solution of unaggregated carbon particles. This means that the particles in the solvent are isolated or at least so little aggregated that the solution is stable. In a stable solution in this case occurs in a storage at room temperature for a period of at least one day, preferably a week or four weeks, no flocculation or precipitation of the carbon particles. To prepare such a solution, the existing aggregates of the carbon particles through Energy input, for example by means of ultrasound, grinding processes or high shear forces are broken. Finally, the solvent is selected after that it can form both the solution of carbon particles and swell the polyurethane surface.

The average particle diameter may also be in a range from> 1 nm to <1000 nm or from> 3 nm to <100 nm. The determination can be made for example by means of scanning electron microscopy or dynamic light scattering.

The solvent may be an aqueous or a nonaqueous solvent. In the latter case, it is preferably a polar, aprotic solvent. In this way, the solvent can interact well with the soft segment domains in the polyurethane. The term "nonaqueous" means that no additional water has been added to the solvent, but excludes the technically unavoidable traces of water, for example up to an amount of <5% by weight, preferably <3% by weight and more preferably <1% by weight. %, not from.

If the solvent is an aqueous solvent, the carbon particles may be deagglomerated in solution by addition of surfactants or other surfactants and kept in solution.

The carbon particles may be dissolved in the solvent in a concentration of, for example,> 0.01% by weight to <20% by weight,> 0.1% by weight to <15% by weight or> 1% by weight to <10% by weight. available.

The contacting of the polyurethane-comprising surface layer with the solution of the carbon particles in step (B) naturally takes place over the surface of the polyurethane.

In the subsequent step (C), the solution of the carbon particles acts on the surface layer. Without being bound by theory, it is believed that the solvent swells at least the soft segment domains in the polyurethane, forms pores in the surface layer, and allows carbon particles to migrate into these pores. In the case of aqueous or aqueous solvents, the swelling of the soft segment domains is favored if there are long polyether segments with a small number of carbon atoms between the ether bridges in the polyurethane. Such domains are hydrophilic enough to swell. The particles may, for example, penetrate into the surface layer to a depth of <150 nm, <100 nm or <50 nm.

In contrast to solution-based processes, the exposure time is chosen such that the polyurethane of the surface layer is not converted into solution. Included here are technically unavoidable dissolution processes in which, for example, <1% by weight, <0.1% by weight or <0.01% by weight of the polyurethane into the solvent. However, the process according to the invention is not a process in which the polymer is first dissolved homogeneously and then, together with nanoparticles, the finished particles are obtained in the matrix by removing the solvent. Rather, the exposure time is chosen so that swelling of the polymer surface can take place. Examples of suitable exposure times are> 1 minute to <360 minutes, preferably> 10 minutes to <90 minutes, more preferably> 3 minutes to <5 minutes.

Finally, step (D) involves stopping the action of the solution of the carbon particles on the surface layer. Thus, therefore, the solution of the carbon particles is separated from the surface layer again. Subsequently, the surface layer can be rinsed to remove adherent solution. This can be done, inter alia, by removing the polyurethane article with the surface layer to be modified from a dipping bath. Thereafter, the article can be rinsed with acetone, for example.

Advantageously, step (D) is followed by a drying step of removing the solvent in the swollen surface layer, closing the pores in the polyurethane and entrapping the carbon particles in the polymer.

The method according to the invention thus offers the possibility of selectively providing the surface layer of a polyurethane article with electrically conductive particles. In this case, the shape of the object is not destroyed by dissolution, so that even finished moldings can be treated. Since the particles are concentrated in the near-surface area of the article, a smaller total amount is needed to obtain an electrically conductive polyurethane surface. Finally, unlike solution-based processes, no large amounts of solvents need to be removed to obtain the final modified polymer. It is also possible to keep the concentration of the carbon particles in a range in which no technically disadvantageous increase in viscosity occurs.

An advantageous application of the method according to the invention is the treatment of polyurethane moldings, which are then to be painted by an electrostatic powder coating or to be galvanized. The electrically conductive particles in the surface layer provide for an improved electrostatic powder application. Another application relates to the treatment of polyurethane moldings for the preparation of an electrodeposition coating. It is also possible to obtain conductive electrode materials or elastic polyurethane capacitors. Furthermore, electronic components or cable sheathing can be provided with an antistatic coating.

In a preferred embodiment of the method according to the invention, the action takes place the solution of the carbon particles on the polyurethane-comprising surface layer using ultrasound and / or heat instead. The energy input by ultrasound and / or heat counteracts the formation of particle aggregates and thus enables higher particle concentrations in the solution. Furthermore, the introduction of the particles into the polyurethane surface layer is accelerated. Advantageously, the ultrasound frequency is ≥20 kHz to <20 MHz and regardless of the power density in the solvent> 1 W / l to <200 W / l. In the case of heating during the action, the temperature may be, for example,> 30 ^° C. to <200 ^° C., preferably> 40 ^° C. to <150 ^° C.

In a further embodiment of the method according to the invention, the carbon particles are not covalently functionalized on their surface. This means that the particles do not carry any additional functional groups covalently attached via further reaction steps on their surface. In particular, the use of oxidants such as

Nitric acid, hydrogen peroxide, potassium permanganate and sulfuric acid or a possible

Mixture of these means for the functionalization of the carbon particles. An advantage of the use of non-covalently functionalized particles is that the ττ electron system of the surface is not disturbed and therefore can contribute unrestrictedly to the electrical conductivity.

Another aspect of the invention is a family of carbon nanotubes, single-walled carbon nanotubes, multi-walled carbon nanotubes, carbon nanohorns, carbon nano-onions, fullerenes, graphite, graphene, carbon fibers, and / or other types of accelerator of the invention. or carbon black. In addition to increasing the electrical conductivity, these particles can also improve mechanical properties of the surface layer, such as elasticity and impact strength.

Carbon nanotubes in the context of the invention are all single-walled or multi-walled carbon nanotubes of the cylinder type, scroll type, multiscroll type or onion-like structure. Preference is given to using multi-wall carbon nanotubes of the cylinder type, scroll type, multiscroll type or mixtures thereof. It is favorable if the carbon nanotubes have a ratio of length to outer diameter of> 5, preferably _dOO.

In contrast to the already mentioned known scroll type carbon nanotubes with only one continuous or interrupted graphene layer, they also exist

Carbon nanotube structures, which consist of several graphene layers, resulting in a

Stack summarized and rolled up. This is called the multiscroll type. These

Carbon nanotubes are described in DE 10 2007 044031 A1, to the full extent

Reference is made. This structure is similar to the simple scroll type carbon nanotubes in comparison to the structure of multiwalled cylindrical carbon nanotubes (cylindrical MWNT) to the structure of the single-walled cylindrical carbon nanotube tubes (cylindrical SWNT).

Unlike the onion type structures, the individual graphene or graphite layers in these carbon nanotubes, as seen in cross-section, evidently run continuously from the center of the carbon nanotubes to the outer edge without interruption. For example, this may allow for improved and faster intercalation of other materials in the tube framework as more open edges than the entry zone of the intercalates are available compared to simple scroll structure carbon nanotubes (Carbon 1996, 34, 1301-3) or onion-like CNTs (Science 1994, 263, 1744-7).

In a preferred embodiment of the method according to the invention, the carbon particles are non-covalently functionalized, multi-walled carbon nanotubes with a diameter of> 3 nm to <100 nm. The diameter here refers to the mean diameter of the nanotubes. It can also be in a range from> 5 nm to <80 nm and advantageously from> 6 nm to <60 nm. The length of the nanotubes is initially not limited. However, it may, for example, be in a range of> 1 μm to <100 μm and advantageously of> 10 μm to <30 μm.

In a further embodiment of the process according to the invention, the polyurethane is obtainable from the reaction of polyisocyanates with polyester polyols and / or polyether polyols. Preferred polyisocyanates are those based on diphenylmethane diisocyanate (MDI) and toluene diisocyanate (TDI). Preferred polyester polyols and polyether polyols have hydroxyl numbers of> 100 mg KOH / g to <150 mg KOH / g. Preferred polyols may furthermore have molar masses in the range of> 250 to <5000 g / mol, preferably> 400 to <3500 g / mol, a functionality of between> 1.8 and <6, preferably between ≥ 1.95 and <3.5. Included in the invention are polyurethanes which are obtainable from prepolymers of the starting compounds mentioned with subsequent chain extension.

In a further embodiment of the process according to the invention, the solvent is selected from the group comprising methanol, ethanol, isopropanol, butanol, ethylene glycol, propylene glycol, butylene glycol, glycerol, hydroquinone, acetone, ethyl acetate, trichlorethylene, trichloroethane, trichloromethane, methylene chloride, cyclohexanone, N, N Dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, N-methyl-2-pyrrolidone, benzene, toluene, chlorobenzene, styrene, Polyesteφolyole, polyether polyols, mixtures of the aforementioned solvents with each other and / or mixtures of the aforementioned solvents with water.

These solvents uniquely combine the ability to form aggregate-free or aggregate-free solutions with the carbon particles while at the same time becoming one Swelling of the polyurethane surface lead. Mixtures of the abovementioned solvents relate to cases in which the solvent in the desired mass fraction is also soluble in water.

In a further embodiment of the method according to the invention, the surface layer comprising the polyurethane is contacted with the solution of the carbon particles by immersion, application, printing, brushing, spraying and / or pouring. By immersing in an immersion bath, for example, objects can be easily completely treated. Also, a continuous process for producing a thus treated polymer film can be easily realized. The printing of polyurethane articles, for example by screen printing, allows the presentation of electrically conductive structures such as printed conductors on the polyurethane article.

In a further embodiment of the method according to the invention, at least in step (C), the surface layer comprising polyurethane is partially covered by a mask. The mask covers parts of the surface and leaves other areas free. In this way, electrically conductive structures on the elastomer surface such as printed conductors and the like can be represented. Another use for the use of a mask is to obtain insulating surfaces on the surfaces of a workpiece.

A further subject of the present invention is a polyurethane layer comprising electrically conductive carbon particles and obtainable by a method according to the invention, wherein the outer surface of the polyurethane layer comprises elevations and depressions with an average height of the elevations of ≥ 50 nm to <500 nm and an average distance between adjacent elevations of> 0.5 μm to <1.5 μm. The height of the elevation is calculated from the vertical distance of the highest point of a survey to the lowest point of an adjacent depression. Figuratively speaking, this corresponds to the distance from Wellenberg to Wellental. The distance between adjacent elevations is then visually the distance between two peaks. In cross section, this may result in a frayed image. The surface of the polyurethane layer may, for example, be in the form of a network of elongate elevations and the corresponding valley-shaped depressions. With regard to the average height of the elevations, it may also be in a range from> 100 nm to <400 nm or from ≥ 150 nm to <300 nm. The average distance between adjacent elevations may also be in a range from> 0.7 μm to <1.2 μm or from> 0.9 μm to <1.0 μm.

The solution with the carbon particles causes swelling of the polyurethane segment structure at the contact surface, which, depending on the polarity of the solution used, leads from swelling of the soft segments to swelling of the hard segments. This allows the Carbon particles interact with the polyurethane and penetrate into the polyurethane matrix. Subsequent evaporation of the solution thus leads to an altered morphology of the polyurethane soft and hard segments on the surface due to the embedding of the carbon particles. In the atomic force microscope image, this can be identified, for example, as undulating elevations and depressions.

The polyurethane layer may, for example, have a specific resistance of> 10 ^-3 ohm cm to <10 ⁸ ohm cm The specific resistance can be determined by the standard DIN IEC 60093 (12) .93 The resistivity of this polyurethane is preferably Layer in a range of> 0.01 ohm cm to <1000000 ohm cm, more preferably from> 0.1 ohm cm to <100000 ohm cm.

The present invention also relates to a polyurethane article having a surface layer comprising electrically conductive carbon particles obtainable by an inventive method, the carbon particles being present in the polyurethane to a depth of <1 μm below the surface. As already stated, the surface layer comprises polyurethane. Advantageously, the particles in this surface layer form a network, so that an electrical conductivity occurs. The particles may also be present to a depth of <500 nm or <150 nm below the surface. Also included in the invention are articles which comprise the polyurethane surface layer provided with carbon particles and additionally comprise further materials. It may, for example, be commodities which at least partially comprise a polyurethane surface and wherein in this surface or polyurethane surface layer, the electrically conductive carbon particles were introduced.

Exemplary of the mentioned polyurethane articles are called polyurethane moldings, which are then to be painted by an electrostatic powder coating or electrocoating or to be galvanized. Other examples include conductive and conductive and elastic electrode materials, generally electronic components or cable sheathing with an antistatic coating.

In one embodiment of the polyurethane article, the carbon particles are present within the polyurethane coating of the surface layer in a proportion of> 0.1 wt% to <5 wt%. The proportion can also be in a range from> 0.5% by weight to <4% by weight or from> 1% by weight to <5% by weight. Ultimately, therefore, this indicates the content of carbon particles in the surface layer. The boundary of the surface layer inside the article, from which the polyurethane material is no longer included in the calculation, is formed by the lowest (innermost) line to which the carbon particles in the polyurethane occur. Within the specified ranges can be the Exceed the percolation limit for the carbon particles, so that the electrical conductivity is greatly improved.

In another embodiment, the polyurethane article, the surface layer comprising the carbon particles have a specific resistance of> ^{10 -3} ohm cm to <10 ⁸ ohm cm. The specific resistance can be determined by the DIN LEC 60093 (12) .93 standard. Preferably, the specific resistance of this polyurethane layer is in a range of> 0.01 ohm cm to <1000000 ohm cm, more preferably from> 0, l ohm cm to <100000 ohm cm.

In a further embodiment of the polyurethane article, the carbon particles are unfunctionalized, multi-walled carbon nanotubes with a diameter of> 3 nm to <100 nm. The diameter here refers to the mean diameter of the nanotubes. It can also be in a range from> 5 nm to <80 nm and advantageously from> 6 nm to <60 nm. The length of the nanotubes is initially not limited. However, it may, for example, be in a range of> 1 μm to <100 μm and advantageously of> 10 μm to <30 μm.

In another embodiment of the polyurethane article, it comprises a first and a second electroconductive carbon particle-containing surface layer, said first and second surface layers being opposed to each other and separated by a polyurethane layer. Due to the manufacturing process, the first and second surface layers are integrally bonded to the separating, electrically insulating polyurethane layer. By such a structure of two dielectric layers separated by a dielectric, an elastic capacitor can be realized.

In a further embodiment of the polyurethane article, this is present as a composite of a carrier material with the polyurethane surface layer comprising electrically conductive carbon particles. Examples of support materials are ceramics, metals, but also other polymers such as polycarbonates or polyolefins. Thus, for example, a metal molding can first be coated with polyurethane and then the polyurethane surface layer can be provided with the carbon particles.

The present invention will be further explained with reference to the following embodiments in conjunction with the figures. Show it:

FIG. 1 a polyurethane article with a three-layer structure

FIG. 2 is an atomic force microscope image of a sample cross-section

FIG. 3 shows another atomic force microscope image of a sample cross-section FIG. 4 shows another atomic force microscope image of a sample cross-section

5 shows a further atomic force microscope Aufhahme a sample cross-section

6 shows a further atomic force microscope Aufhahme a sample surface

FIG. 7 shows another AFM image of a sample surface

EXAMPLES

Starting materials, polyurethane production and general implementation:

Polyol: Polyether polyol having an OH number of 112 mg KOH / mg and a viscosity of 140 mPa · s at 25 ⁰ C.

Catalyst: dibutyltin dilaurate (0.02% by weight), DABCO 33-LV® (0.54% by weight, Air Products)

Isocyanate: DESMODUR® CD-S: modified isocyanate based on diphenylmethane 4,4'-diisocyanate with an NCO content of 29.0 to 30.0% by weight and a viscosity of 20 to 50 mPa-s at 25 ⁰ C

Carbon particles: Multi-Walled Carbon Nanotubes (BAYTUBES® C 150 P)

Dip solution: Dispersion of BAYTUBES® C 150 P in a solvent

The aforementioned components polyol, catalyst and isocyanate were mixed together at room temperature so that the ratio was 105. The dipping solution was prepared by sonicating the carbon particles in the ultrasonic bath and used immediately. To functionalize the polyurethane surface, the samples were completely immersed in the solution, rinsed briefly with acetone after removal and freed of excess solvent at elevated temperature.

Example 1 (in NMP, with ultrasound):

A sample of a polyurethane elastomer (7 x 7 x 0.2 cm) was completely immersed in a solution of 1% by weight of BAYTUBES® C 150 P in N-methyl-2-pyrrolidone. The exposure time was 0.5 h under sonication in an ultrasonic bath and additionally 5.5 h without sonication at room temperature. The sample was rinsed briefly with acetone and freed of solvents at 100 ^° C. in a drying oven. The measured surface resistance ranged from 10 ² to 10 ⁴ ohm cm. Closer examination by AFM revealed the incorporation of the nanotubes into the polyurethane surface to a penetration depth of approximately 0.5 μm (FIG. 3). _

Corresponding conductivity measurements (TUNA) also showed conductivity at the PU surface (FIG. 2).

Example 2 (in acetone, with ultrasound):

A specimen of a polyurethane elastomer (7 × 7 × 0.2 cm) was immersed completely in a solution of 0.5% by weight of BAYTUBES® C 150 P in acetone under sonication in an ultrasonic bath. The exposure time was 1 h, the temperature of the dipping solution was 45 ° C. The sample was rinsed briefly with acetone and freed from solvent at 50 ^° C. in a drying oven. The measured surface resistance was in the range of 10 ⁵ ohm cm.

Example 3 (in acetone, without ultrasound):

A sample of a polyurethane elastomer (7 x 7 x 0.2 cm) was immersed in a solution of 0.5% by weight of BAYTUBES® C 150 P in acetone. The exposure time was 1 h, the temperature of the dip solution was 23 ⁰ C. The sample was rinsed briefly with acetone and freed of solvent at 50 ⁰ C in a drying oven. The measured surface resistance was in the range of 10 ⁶ ohm cm.

FIG. 1 shows schematically a polyurethane article according to the invention with a three-layer structure. Starting from a polyurethane workpiece, carbon nanotubes were introduced into the top (1) and bottom (2) surface layers of the polyurethane. These nanotubes are represented by dashes or dots in the respective layers (I ₅ 2). It can be seen that the nanotubes have a limited penetration depth into the surface layers. The surface layers are separated by a nanotube-free polyurethane layer (3). Due to the manufacturing process of the polyurethane article is still in one piece with respect to the surface layers (1, 2) constructed and the surface layers are materially connected to the nanotube-free layer (3). The polyurethane article shown may, with suitable dimensions, serve, for example, as a film-shaped condenser.

A sample of the polyurethane article obtained in Example 1 was examined by atomic force microscope (AFM) imaging. Information on the presence and location of the carbon nanotubes is provided by the Tunnel AFM Mount (TUNA) in FIG. 2. This is a sample cross-section. The width of the displayed image section was 10 μm. The left part of the image contains matrix material into which the sample has been enclosed in order to prepare the cross sections. In the right part is the unchanged polyurethane material. In between runs, recognizable as bright points, the surface layer interspersed with the tunnel current-conducting carbon nanotubes.

FIG. 3 and 4 show different image sections of the same sample in cross-sectional view and - 1 - in phase-sensitive mode. The width of the displayed image section was 2.5 μm. The left-hand part of the images contains matrix material into which the sample was enclosed in order to prepare the cross-sections. In the right part is the unchanged polyurethane material. In between, the surface layer penetrated by carbon nanotubes passes. The phase-sensitive recordings in FIG. 3 and 4 clearly show the embedded in the surface layer carbon nanotubes as bright lines. Overall, it is thus shown that the nanotubes are also present below the surface of the polyurethane.

FIG. 5 shows a further cross-sectional view with a width of the image section of 5 μm. The embedded in the surface layer carbon nanotubes can be seen as well visible bright lines.

Images of a plan view of the sample surface are shown in FIG. 6 and 7 are shown. The height recording in FIG. Fig. 6 shows a structure crossed by elevations and valley-shaped depressions. The width of the displayed image section was 2.5 μm. In the corresponding phase-sensitive view in FIG. Figure 7 shows carbon nanotubes accessible on the sample surface as bright lines.

Claims

claims

A method of introducing electrically conductive particles into a surface layer comprising polyurethane, comprising the steps of:

(A) providing a solution of non-aggregated carbon particles having a mean particle diameter of> 0.3 nm to <3000 nm in a solvent capable of causing the swelling of a surface layer comprising polyurethane;

(C) Exposing the solution of carbon particles to the polyurethane

Surface layer for a time not sufficient to dissolve the polyurethane in solution;

2. The method according to claim 1, wherein the action of the solution of the carbon particles takes place on the polyurethane-comprising surface layer using ultrasound and / or heat.

3. The method according to claim 1, wherein the carbon particles are not covalently functionalized on their surface.

4. The method of claim 1, wherein the carbon particles are selected from the group consisting of carbon nanotubes, single-walled carbon nanotubes, multi-walled carbon nanotubes, carbon nanohorns, carbon nano-onions, fullerenes, graphite, graphene, carbon fibers and / or carbon black.

5. The method according to claim 4, wherein the carbon particles are non-covalently functionalized, multi-walled carbon nanotubes with a diameter of ≥3 nm to <100 nm.

6. The method according to claim 1, wherein the solvent is selected from the group comprising methanol, ethanol, isopropanol, butanol, ethylene glycol, propylene glycol, butylene glycol, glycerol, hydroquinone, acetone, ethyl acetate, trichlorethylene, trichloroethane, trichloromethane, methylene chloride, cyclohexanone, N, N-dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, N-methyl-2-pyrrolidone, benzene, toluene, chlorobenzene, styrene, polyesterpolyols, polyetherpolyols, mixtures of the abovementioned solvents. and / or mixtures of the abovementioned solvents with water.

7. A method according to claim 1, wherein the contacting of the surface layer comprising polyurethane with the solution of the carbon particles is carried out by dipping, applying, printing, brushing, spraying and / or pouring.

8. The method according to claim 1, wherein at least in step (C) the polyurethane-comprising surface layer is partially covered by a mask.

A polyurethane layer comprising electrically conductive carbon particles and obtainable by a method according to claim 1, wherein the outer surface of the polyurethane layer comprises bumps and depressions having an average height of the bumps of> 50 nm to <500 nm and an average distance between adjacent elevations of> 0.5 microns to <1.5 microns.

10. A polyurethane article comprising a surface layer (1) comprising an electrically conductive carbon particle obtainable by a process according to claim 1, wherein the carbon particles are present in the polyurethane to a depth of <1 μm below the surface.

11. A polyurethane article according to claim 10, wherein the carbon particles are present within the polyurethane material of the surface layer (1) comprising them in a proportion of> 0.1% by weight to <5% by weight.

12. The polyurethane article according to claim 10, wherein the carbon particle-comprising layer (1) has a resistivity of> 10 ^-3 ohm cm to <10 ⁸ ohm cm at the surface.

The polyurethane article of claim 10, wherein the carbon particles are non-covalently functionalized, multi-walled carbon nanotubes having a diameter of> 3 nm to <100 nm.

14. A polyurethane article according to claim 10 comprising a first (1) and a second (2) electrically conductive carbon particles comprising a surface layer, said first (1) and second (2) surface layers being disposed opposite each other and penetrated by a polyurethane layer (3). are separated from each other.

15. Polyurethane article according to claim 10, present in the form of a composite of a carrier material with the polyurethane surface layer comprising electrically conductive carbon particles.